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Deforestation, over-development of water resources and population growth have contributed to degeneration of vegetation in the Heihe River Basin in northwest China. Salts and water contents are the most important factors affecting the growth of vegetation in this arid area. This study was conducted to determine soluble salt levels of soils in the unsaturated zone and the hydrochemistry of groundwater at 14 sites in this region. Concentrations of soluble ions in the soils deceased with depth. Soil ion contents increased at depths below the root system of native plants. Sulfate was the dominant anion in both the unsaturated zone and the groundwater. Total dissolved solids (TDS) in groundwater ranged from less than 1 g/L in the middle reaches of the watershed to about 10 g/L in the arid lower reaches. In the middle and upper reaches of the watershed, salinity in soil and groundwater decreased. Groundwater was highly variable in hydrochemistry. The lower reaches was predominated by SO4-Na center dot CoMg and SO4-Mg center dot CoNa type water, whereas in the middle reaches groundwater is characterized by lower TDS and HCO3-dominated type water. Evapotranspiration is responsible for occurrence of the soluble salts in the soil profiles. Dissolution is the dominant chemical process in the middle reaches, whereas evapotranspiration prevails in the lower reaches of the Heihe River.